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United States Patent |
5,746,818
|
Yatake
|
May 5, 1998
|
Pigment ink composition capable of forming image having no significant
bleeding or feathering
Abstract
An ink for ink jet recording is provided which can form a record having a
high color density, free from the occurrence of bleeding or feathering
even on recycled paper, and possessing water resistance. An ink
composition comprising a pigment dispersible and/or soluble in water
without the aid of any dispersant and a glycol ether selected from the
group consisting of diethylene glycol mono-n-butyl ether, triethylene
glycol mono-n-buityl ether, propylene glycol mono-n-butyl ether, and
dipropylene glycol mono-n-butyl ether can realize a print having no
significant bleeding or feathering. Further, a high-quality image having
much less bleeding or feathering can be realized by an ink jet recording
method wherein a reaction solution, containing a reactant, capable of
breaking the state of dispersion and/or dissolution of a pigment in the
ink composition is brought into contact with the ink composition.
Inventors:
|
Yatake; Masahiro (Suwa, JP)
|
Assignee:
|
Seiko Epson Corporation (Tokyo-To, JP)
|
Appl. No.:
|
705287 |
Filed:
|
August 29, 1996 |
Foreign Application Priority Data
| Aug 31, 1995[JP] | 7-224330 |
| Oct 06, 1995[JP] | 7-260585 |
| Jan 19, 1996[JP] | 8-007216 |
| Apr 16, 1996[JP] | 8-094568 |
| Aug 01, 1996[JP] | 8-204008 |
Current U.S. Class: |
106/31.86; 106/31.28; 106/31.52; 106/31.89; 347/96; 347/100; 347/101 |
Intern'l Class: |
C09D 011/02 |
Field of Search: |
347/101,100,96
106/20 R,23 R,31.86,31.89,31.28,31.52
|
References Cited
U.S. Patent Documents
4517794 | May., 1985 | Ohta et al. | 106/20.
|
5417747 | May., 1995 | Arata et al. | 106/20.
|
5441561 | Aug., 1995 | Chujo et al. | 106/20.
|
Foreign Patent Documents |
0441987 | Aug., 1991 | EP.
| |
0635380 | Jan., 1995 | EP.
| |
Other References
Patent Abstract of Japan JP 6-128,517 of May 1994.
Patent Abstract of Japan JP 5-339,516 of Dec. 1992.
|
Primary Examiner: Jones; Deborah
Attorney, Agent or Firm: Ladas & Parry
Claims
What is claimed is:
1. A recording method comprising the step of:
depositing a reactant-containing reaction solution and an ink composition
onto a recording medium to conduct printing, the ink composition
comprising a pigment a glycol ether, and water the pigment being
dispersible and/or soluble in water without the aid of any dispersant, the
glycol ether being one member or a mixture of two or more members selected
from the group consisting of diethylene glycol mono-n-butyl ether,
triethylene glycol mono-n-butyl ether, propylene glycol mono-n-butyl
ether, and dipropylene glycol mono-n-butyl ether, the reactant being a
material which can break a state of dispersion and/or dissolution of the
pigment.
2. The recording method according to claim 1, wherein the reactant is a
cationic material or salt.
3. The recording method according to claim 2, wherein the cationic material
is selected from the group consisting of primary, secondary, tertiary, and
quaternary amines and compounds having in molecule ammonium, phosphorus,
and phosphonium.
4. The recording method according to claim 2, wherein the salt is a
polyallylamine, polyethyleneimine, polyvinyl pyrrolidone, polyvinyl
imidazole, polyvinyl pyridine, ionene, or polydialkylallylammonium salt.
5. The recording method according to claim 2, wherein the salt is formed
with as a cation species a metal ion of alkali metal, an alkaline earth
metal, aluminum, zinc, chromium, copper, nickel, or iron.
6. The recording method according to claim 1, wherein the reaction solution
contains a colorant and serves also as an ink composition.
7. The recording method according to claim 1, wherein, after the deposition
of the reaction solution on the recording medium, the ink composition is
printed on the recording medium.
8. The recording method according to claim 7, wherein the time taken from
the deposition of the reaction solution onto the recording medium to the
initiation of the printing of the ink composition is not more than 3 sec.
9. The recording method according to claim 1, wherein, after the printing
of the ink composition on the recording medium, the reaction solution is
deposited onto the recording medium.
10. The recording method according to claim 1, wherein the reaction
solution is combined with the ink composition immediately before or after
the deposition onto the recording medium to conduct printing.
11. The recording method according to claim 1, wherein the reaction
solution further contains a glycol ether.
12. The recording method according to claim 1, wherein the reaction
solution further contains an acetylene glycol surfactant.
13. The recording method according to claim 12, wherein the acetylene
glycol surfactant in the reaction solution is in the range of 0.1 to 5% by
weight.
14. The recording method according to claim 1, wherein the reaction
solution and/or the ink composition are ejected as droplets through fine
nozzles and the droplets are deposited onto the recording medium.
15. The recording method according to claim 14, wherein, during a period
wherein the droplets of the ink composition is not under ejection, the ink
composition is moved to vibrate within the fine nozzle to such an extent
that it is not ejected as droplets through the nozzle.
16. The recording method according to claim 15, wherein the pigment content
of the ink composition is 5 to 15% by weight.
17. The recording method according to claim 1, wherein the amount of the
ink composition used is 50 to 200% based on the amount of the reaction
solution used.
18. A recorded medium obtained by printing using a recording method
according to claim 1.
19. The method according to claim 1, wherein the pigment has been treated
to bond at least one functional group selected from the group consisting
of carbonyl, carboxyl, hydroxyl, and sulfonyl groups or a salt thereof
onto the surface thereof, wherein the pigment is dispersed and/or
dissolved in water without the aid of any dispersant.
20. The method according to claim 1, wherein the pigment is present in the
ink composition in the range of 2 to 15% by weight.
21. The method according to claim 1, wherein the glycol ether is present in
the ink composition in the range of 3 to 30% by weight.
22. The method according to claim 1, wherein the ink composition further
comprises an acetylene glycol surfactant.
23. The method according to claim 22, wherein the acetylene glycol
surfactant is present in the ink composition in the range of 0.1 to 5% by
weight.
24. The method according to claim 1, wherein the ink composition further
comprises a glycol.
25. The method according to claim 24, wherein the glycol is present in the
ink composition in the range of 3 to 25% by weight.
26. The method according to claim 1, wherein the ink composition further
comprises a dye.
27. The method according to claim 26, wherein the dye is a water-soluble
dye represented by the following general formula (I) or (II):
##STR4##
wherein A represents POOM or COOM, X and Y each independently represent an
alkoxy or alkyl group, M represents an alkali metal, H, or NH.sub.4, or an
organic amine; and
##STR5##
wherein M represents an alkali metal, H, or NH.sub.4, or an organic amine,
m is 1 or 2 and n is 0 or 1.
28. The method according to claim 27, wherein the amount of the
water-soluble dye in the ink composition is 50 to less than 200% by weight
based on the pigment.
29. The method according to claim 11, wherein the ink composition further
comprises a surfactant and/or a regulated polymerization water-soluble
resin.
30. The method according to claim 29, wherein the surfactant and/or the
regulated polymerization type water-soluble resin can promote or stabilize
the dispersion of the pigment.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an ink, for ink jet recording, which can
form a high-quality print having no significant bleeding or feathering on
plain paper, recycled paper, or coat paper.
2. Background Art
Ink jet recording is a recording method wherein an ink is ejected as small
droplets through a fine nozzle and deposited onto the surface of a
recording medium to record letters or figures on the recording medium. An
ink used in such ink jet recording is required to have properties
including the formation of a record having a good drying property and free
from bleeding or feathering and uniform recording on the surface of
recording media irrespective of the type of the recording media.
What is to be noted here as a problem associated with the above properties
is that, when paper is used as the recording medium, a difference in
penetration of an ink between fibers constituting the paper is likely to
cause bleeding or feathering. The problem of bleeding or feathering is
more significant on the recycled paper which, in recent years, has become
extensively used from the viewpoint of environmental problems. This is
because the recycled paper is an aggregate of various paper components
different from one another in rate of ink penetration. The bleeding or
feathering due to the difference in penetration rate.
Various ink compositions have hitherto been proposed in order to prevent
bleeding or feathering.
For example, Japanese Patent Publication No. 2907/1990 proposes the
utilization of a glycol ether as a wetting agent, Japanese Patent
Publication No. 15542/1989 proposes the utilization of a water-soluble
organic solvent, and Japanese Patent Publication No. 3837/1990 proposes
the utilization of a dye dissolution accelerator. U.S. Pat. No. 5,156,675
proposes the addition of diethylene glycol monobutyl ether in order to
improve the penetration of the ink, U.S. Pat. No. 5,183,502 proposes the
addition of Surfynol 465 as an acetylene glycol surfactant, and U.S. Pat.
No. 5,196,056 proposes the addition of both diethylene glycol monobutyl
ether and Surfynol 465. In this connection, it should be noted that
diethylene glycol mono-n-butyl ether is known also as "butyl carbitol" and
described in, for example, U.S. Pat. No. 3,291,580. Further, the use of
diethylene glycol ether has been studied in U.S. Pat. No. 2,083,372.
Further, Japanese Patent Laid-Open No. 147861/1981 proposes the combined
use of a pigment and triethylene glycol monomethyl ether.
Furthermore, heating of recording paper has been studied for reducing the
bleeding or feathering. Heating of recording paper at the time of
recording poses problems including that much time is necessary in order to
raise the temperature of a heating section in the recording apparatus to a
predetermined temperature. Moreover, the power consumption of the body of
the recording apparatus is increased. Sometimes, recording media, such as
recording paper, are damaged by the heat.
In the case of inks using a pigment, methyl ethers as disclosed in Japanese
Patent Laid-Open No. 147861/1981 are, in many cases, used as the glycol
ethers for inhibiting the penetration of the ink.
However, a need still exits for an ink composition which can realize a
high-quality image having no significant bleeding or feathering.
An ink composition comprising a combination of a pigment with a butyl ether
of a glycol, such as diethylene glycol monobutyl ether, has not been
proposed in the art, so far as the present inventors know.
SUMMARY OF THE INVENTION
We have now found that an ink composition comprising a pigment and a butyl
ether of a specific glycol, such as diethylene glycol monobutyl ether can
effectively inhibit the bleeding or feathering, realizing a high-quality
image. Further, we have found that the use of the above ink composition in
a recording method using the so-called "two liquids", wherein a reaction
solution and an ink composition are deposited to conduct printing, can
provide a better image.
Accordingly, an object of the present invention is to provide an ink
composition which can realize a good image on plain paper and even on
recycled paper.
Another object of the present invention is to provide a recording method
which can realize a good image on plain paper and even on recycled paper.
According to one aspect of the present invention, there is provided an ink
composition comprising at least a pigment, a glycol ether, and water, the
pigment being dispersible and/or soluble in water without the aid of any
dispersant, the glycol ether being one member or a mixture of at least two
members selected from the group consisting of diethylene glycol
mono-n-butyl ether, triethylene glycol mono-n-butyl ether, propylene
glycol mono-n-butyl ether, and dipropylene glycol mono-n-butyl ether.
According to another aspect of the present invention, there is provided a
recording method comprising the step of: depositing a reactant-containing
reaction solution and an ink composition onto a recording medium to
conduct printing, wherein an ink composition according to the present
invention is used as the ink composition, and the reactant can break the
state of dispersion and/or dissolution of the pigment.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram showing an ink jet recording apparatus according to the
present invention, wherein a recording head is provided independently of
an ink tank and an ink composition and a reaction solution are supplied
into the recording head through an ink tube;
FIG. 2 is an enlarged view of a nozzle face in a recording head, wherein 1b
designates a nozzle face for a reaction solution and c designates a nozzle
face for an ink composition;
FIG. 3 is an explanatory view for ink jet recording using the recording
head shown in FIG. 2, wherein numeral 31 designates a reaction solution
deposited area and numeral 32 designates a printed area with an ink
composition printed on the reaction solution deposited area;
FIG. 4 is a diagram showing another embodiment of a recording head
according to the present invention, wherein all ejection nozzles are
arranged in lateral direction; and
FIG. 5 is a diagram showing an ink jet recording apparatus according to the
present invention, wherein an recording head is integral with an ink tank.
DETAILED DESCRIPTIONS OF THE INVENTION
Ink composition
The ink composition according to the present invention is used in a
recording system using an ink composition. The recording system using an
ink composition include, for example, an ink jet recording system, a
recording system using writing utensils, such as pens, and other various
printing systems. Particularly preferably, the ink composition according
to the present invention is used in the ink jet recording system. The ink
composition according to the present invention comprises at least a
pigment, a glycol ether, and water.
The pigment used in the present invention is dispersible and/or soluble in
water without the aid of any dispersant. Further, in the present
invention, the term "glycol ether" refers to one member or a mixture of at
least two members selected from the group consisting of diethylene glycol
mono-n-butyl ether, triethylene glycol mono-n-butyl ether, propylene
glycol mono-n-butyl ether, and dipropylene glycol mono-n-butyl ether.
The pigment which may be preferably used in the present invention has been
subjected to surface treatment to bond at least one functional group
selected from the group consisting of carbonyl, carboxyl, hydroxyl, and
sulfonyl groups or a salt thereof onto the surface thereof, permitting the
pigment to be dispersed and/or dissolved in water without the aid of any
dispersant. Specifically, such a pigment may be prepared by grafting the
functional group or a molecule containing the functional group onto the
surface of carbon black by physical treatment, such as treatment using
vacuum plasma, or chemical treatment. In the present invention, a single
kind of the functional group or a plurality of kinds of the functional
groups may be grafted onto one carbon black particle. The kind of the
functional group and the degree of grafting may be suitably determined by
taking into consideration the dispersion stability in the ink, the color
density, the drying property on the front face of the ink jet recording
head and the like.
In the present invention, the state of a pigment stably present in water
without the aid of any dispersant is expressed as "being dispersed and/or
dissolved." There are many cases where it is difficult to distinguish the
state of dissolution from the state of dispersion. In the present
invention, so far as a pigment is stably present in water without the aid
of any dispersant, such a pigment may be used regardless of whether the
pigment is present in a dispersed state or a dissolved state. Therefore,
in the present specification, although a pigment which can be stably
present in water without the aid of any dispersant is often referred to as
a "water-soluble pigment," this does not mean the exclusion of pigments in
a dispersed state.
The above pigments which may be preferably used in the present invention
can be prepared, for example, by a method described in Japanese Patent
Laid-Open No. 3498/1986. Further, commercially available products may be
used as the above pigment, and preferred examples thereof include Microjet
CW1 or CW2 manufactured by Orient Chemical Industries, Ltd.
The amount of the pigment added to the ink composition is preferably 2 to
15% by weight, more preferably about 4 to 10% by weight.
The glycol ether added, in combination with the pigment, to the ink
composition of the present invention is selected from diethylene glycol
mono-n-butyl ether, triethylene glycol mono-n-butyl ether, propylene
glycol mono-n-butyl ether, and dipropylene glycol mono-n-butyl ether.
In general, a pigment is dispersed with the aid of a dispersant in an ink
composition.
Experiments conducted by the present inventors, the addition of a glycol
ether to an ink composition containing a pigment for the purpose of
improving the penetration of the ink have revealed that a stable
dispersion is broken causing agglomeration or thickening of the ink.
In order to improve the penetration of the ink composition containing a
pigment dispersible and/or soluble in water without the aid of any
dispersant, we have attempted to add a glycol ether. As a result, they
have found that the addition of the above four glycol ethers can
effectively prevent bleeding or feathering. This is surprising because
other glycol ethers than the above four glycol ethers cannot reduce or can
only slightly reduce the bleeding or feathering.
The amount of the glycol ether added to the ink composition according to
the present invention is preferably about 3 to 30% by weight, more
preferably about 5 to 10% by weight.
According to a preferred embodiment of the present invention, some of the
above glycol ethers have low water solubility. Therefore, preferably, the
following component is added to improve the solubility. Components usable
herein include diols and glycols, such as other glycol ethers having high
water solubility, thiodiglycol, 1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, propylene glycol, dipropylene glycol, and tripropylene
glycol; and surfactants.
According to a preferred embodiment of the present invention, the ink
composition contains an acetylene glycol surfactant. Examples of acetylene
glycol surfactants include 2,4,7,9-tetramethyl-5-decyne-4,7-diol,
3,6-dimethyl-4-octyne-3,6-diol, and 3,5-dimethyl-1-hexyne-3-ol, for
example, Surfynol 104, 82, 465, 485 and TG manufactured by Nissin Chemical
Industry Co., Ltd. In particular, the use of Surfynol 104 or Tg can offer
good record quality.
The amount of the acetylene glycol surfactant added is preferably about 0.1
to 5% by weight, more preferably about 0.5 to 1.5% by weight, based on the
ink composition. The addition of the acetylene glycol in the above amount
results in further reduced bleeding or feathering.
Some acetylene glycol surfactants, for example, Surfynol 104 and TG, have
low solubility in water due to low HLB. The low solubility can be improved
by adding a component, such as a glycol ether, a glycol, or a surfactant,
to the ink composition.
According to a preferred embodiment of the present invention, the ink
composition contains a glycol in order to prevent clogging of nozzles of
the ink jet recording head. Preferred glycols include water-soluble
glycols, and examples thereof include ethylene glycol, diethylene glycol,
triethylene glycol, propylene glycol, dipropylene glycol, tripropylene
glycol, polyethylene glycol having a molecular weight of not more than
600, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,4
-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin,
meso-erythritol, and pentaerythritol.
Other additives which are further useful for preventing the clogging of
nozzles include thiodiglycol, 1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, propylene glycol, dipropylene glycol, tripropylene glycol,
neopentyl glycol, 2-methyl-2,4-pentanediol, trimethylolpropane, and
trimethylolethane. They may be used alone or as a mixture of two or more.
The amount of the above component which may be added in order to prevent
clogging may be properly determined so as to attain the contemplated
purpose. For example, in the case of a glycol, the amount is preferably
about 3 to 25% by weight.
According to a preferred embodiment, the ink composition of the present
invention may further comprise a water-soluble organic solvent in order to
improve the solubility of the glycol ether having low solubility in water,
to improve the penetration of the ink into a recording medium, for
example, paper, or to prevent clogging of the nozzle. Preferred examples
of the water-soluble organic solvent include: alkyl alcohols having 1 to 4
carbon atoms, such as ethanol, methanol, butanol, propanol and
isopropanol; glycol ethers, such as ethylene glycol monomethyl ether,
ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene
glycol monomethyl ether acetate, diethylene glycol monomethyl ether,
diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether,
ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl
ether, ethylene glycol mono-n-butyl ether, ethylene glycol-mono-t-butyl
ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxy butanol,
propylene glycol monomethyl ether, propylene glycol monoethyl ether,
propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether,
propylene glycol mono-iso-propyl ether, dipropylene glycol monomethyl
ether, dipropylene glycol monoethyl ether, dipropylene glycol
mono-n-propyl ether, and dipropylene glycol mono-iso-propyl ether;
formamide; acetamide; dimethylsulfoxide; sorbitol; sorbitan; acetin;
diacetin; triacetin; and sulfolane. The amount of the water-soluble
organic solvent added is preferably about 5 to 60% by weight based on the
total amount of the ink composition.
According to a preferred embodiment of the present invention, the ink
composition may contain other surfactant(s) in order to regulate the
penetration of the ink composition. Preferably, this surfactant has good
compatibility with the ink composition. Among surfactants, those having
high penetration and stability are preferred. Preferred specific examples
thereof include amphoteric surfactants and nonionic surfactants.
Amphtoteric surfactants include, for example, lauryldimethylaminoacetic
acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine,
coconut oil fatty acid amide propyldimethylaminoacetic acid betaine,
polyoctylpolyaminoethylglycine and other imidazoline derivatives. Examples
of nonionic surfactants include ether nonionic surfactants, such as
polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenol ether,
polyoxyethylene dodecylphenyl ether, polyoxyethylene alkylallyl ether,
polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene
alkyl ethers and polyoxyalkylene alkyl ether, ester nonionic surfactants,
such as polyoxyethyleneoleic acid, polyoxyethyleneoleic acid esters,
polyoxyethylenedistearic acid esters, sorbitan laurate, sorbitan
monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene
monooleate and polyoxyethylene stearate, and other nonionic surfactants,
such as fluorosurfactants including fluoroalkyl esters, and salts of
perfluoroalkylcarboxylic acids.
According to a preferred embodiment of the present invention, the ink
composition may further comprise a saccharide. The addition of the
saccharide can effectively prevent the clogging of the nozzle in the ink
jet recording head. The saccharide may be any of monosaccharides and
polysaccharides, and examples thereof include glucose, mannose, fructose,
ribose, xylose, arabinose, lactose, galactose, aldonic acid, glucitose,
maltose, cellobiose, sucrose, trehalose, and maltotriose and, further,
alginic acid and salts thereof, cyclodextrins, and celluloses. The amount
of the saccharide added is preferably about 1 to 10% by weight, more
preferably 3 to 7%.
Further, according to a preferred embodiment of the present invention, the
ink composition may contain various additives for the purpose of improving
various properties of the ink composition, such as antiseptic agents,
mildewproofing agents, pH adjustors, dye dissolution assistants,
antioxidants, conductivity modifiers, surface tension modifiers, and
oxygen-absorbing agents.
Specific examples of the antiseptic and mildewproofing agents include
sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide,
sodium sorbicate, sodium dehydroacetate and 1,2-dibenzothiazolin-3-one
(Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL-2 and Proxel TN,
manufactured by ICI).
Examples of the pH adjustor, dye dissolution assistant, and antioxidant
include amines, such as a diethanolamine, triethanolamine, propanolamine,
and morpholine and modification products thereof, inorganic salts, such as
potassium hydroxide, sodium hydroxide, and lithium hydroxide, ammonium
hydroxide, quaternary ammonium hydroxide (such as tetramethylammonium),
carbonates and phosphates, such as potassium carbonate, sodium carbonate,
and lithium carbonate, or N-methyl-2-pyrrolidone, ureas, such as urea,
thiourea, and tetramethylurea, allophanates, such as allophanate and
methyl allophanate, biurets, such as biuret, dimethylbiuret, and
tetramethylbiuret, and L-ascorbic acid and salts thereof.
Further, the ink composition according to the present invention may contain
antioxidants and ultraviolet absorbers. Examples of commercially available
products thereof include Tinuvin 328, 900, 1130, 384, 292, 123, 144, 622,
770, and 292, Irgacor 252, 153, Irganox 1010, 1076, 1035, and MD 1024,
manufactured by CIBA-GEIGY.
Furthermore, the ink composition of the present invention may contain
viscosity modifiers, and specific examples thereof include rosins, alginic
acids, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl
cellulose, hydroxyethyl cellulose, methyl cellulose, polyacrylates,
polyvinylpyrrolidone, and gum arabic starch.
According to a preferred embodiment, the ink composition of the present
invention may further comprise a dye in order to improve the color
development of the pigment or to improve the color density. Examples of
dyes usable herein include direct dyes, acid dyes, basic dyes, reactive
dyes, and food dyes.
Specific preferred examples of dyes usable in the present invention
include:
direct dyes, for example, C.I. Direct Black 2, 4, 9, 11, 14, 17, 19, 22,
27, 32, 36, 41, 48, 51, 56, 62, 71, 74, 75, 77, 78, 80, 105, 106, 107,
108, 112, 113, 117, 132, 146, 154, 168, 171, and 194, C.I. Direct Yellow
1, 2, 4, 8, 11, 12, 24, 26, 27, 28, 33, 34, 39, 41, 42, 44, 48, 50, 51,
58, 72, 85, 86, 87, 88, 98, 100, 110, 127, 135, 141, 142 and 144, C.I.
Direct Orange 6, 8, 10, 26, 29, 39, 41, 49, 51, 62 and 102, C.I. Direct
Red 1, 2, 4, 8, 9, 11, 13, 15, 17, 20, 23, 24, 28, 31, 33, 37, 39, 44, 46,
47, 48, 51, 59, 62, 63, 73, 75, 77, 79, 80, 81, 83, 84, 85, 87, 89, 90,
94, 95, 99, 101, 108, 110, 145, 189, 197, 224, 225, 226, 227, 230, 250,
256 and 257, C.I. Direct Violet 1, 7, 9, 12, 35, 48, 51, 90 and 94, C.I.
Direct Blue 1, 2, 6, 8, 12, 15, 22, 25, 34, 69, 70, 71, 72, 75, 76, 78,
80, 81, 82, 83, 86, 87, 90, 98, 106, 108, 110, 120, 123, 158, 163, 165,
192, 193, 194, 195, 196, 199, 200, 201, 202, 203, 207, 218, 236, 237, 239,
246, 258 and 287, C.I. Direct Green 1, 6, 8, 28, 33, 37, 63 and 64, and
C.I. Direct Brown 1A, 2, 6, 25, 27, 44, 58, 95, 100, 101, 106, 112, 173,
194, 195, 209, 210 and 211;
acid dyes, for example, C.I. Acid Black 1, 2, 7, 16, 17, 24, 26, 28, 31,
41, 48, 52, 58, 60, 63, 94, 107, 109, 112, 118, 119, 121, 122, 131, 155
and 156, C.I. Acid Yellow 1, 3, 4, 7, 11, 12, 13, 14, 17, 18, 19, 23, 25,
29, 34, 36, 38, 40, 41, 42, 44, 49, 53, 55, 59, 61, 71, 72, 76, 78, 79,
99, 111, 114, 116, 122, 135, 142, 161 and 172, C.I. Acid Orange 7, 8, 10,
19, 20, 24, 28, 33, 41, 45, 51, 56 and 64, C.I. Acid Red 1, 4, 6, 8, 13,
14, 15, 18, 19, 21, 26, 27, 30, 32, 34, 35, 37, 40, 42, 44, 51, 52, 54,
57, 80, 82, 83, 85, 87, 88, 89, 92, 94, 97, 106, 108, 110, 111, 114, 115,
119, 129, 131, 134, 135, 143, 144, 152, 154, 155, 172, 176, 180, 184, 186,
187, 249, 254, 256, 289, 317 and 318, C.I. Acid Violet 7, 11, 15, 34, 35,
41, 43, 49, 51 and 75, C.I. Acid Blue 1, 7, 9, 15, 22, 23, 25, 27, 29, 40,
41, 43, 45, 51, 53, 55, 56, 59, 62, 78, 80, 81, 83, 90, 92, 93, 102, 104,
111, 113, 117, 120, 124, 126, 138, 145, 167, 171, 175, 183, 229, 234, 236
and 249, C.I. Acid Green 3, 9, 12, 16, 19, 20, 25, 27, 41 and 44, and C.I.
Acid Brown 4 and 14;
basic dyes, for example, C.I. Basic Black 2 and 8, C.I. Basic Yellow 1, 2,
11, 14, 21, 32 and 36, C.I. Basic Orange 2, 15, 21 and 22, C.I. Basic Red
1, 2, 9, 12, 13 and 37, C.I. Basic Violet 1, 3, 7, 10 and 14, C.I. Basic
Blue 1, 3, 5, 7, 9, 24, 25, 26, 28 and 29, C.I. Basic Green 1 and 4, and
C.I. Basic Brown 1 and 12.
reactive dyes, for example, C.I. Reactive Black 1, 3, 5, 6, 8, 12 and 14,
C.I. Reactive Yellow 1, 2, 3, 12, 13, 14, 15 and 17, C.I. Reactive Orange
2, 5, 7, 16, 20 and 24, C.I. Reactive Red 6, 7, 11, 12, 15, 17, 21, 23,
24, 35, 36, 42, 63, 66, 84 and 184, C.I. Reactive Violet 2, 4, 5, 8 and 9,
C.I. Reactive Blue 2, 5, 7, 12, 13, 14, 15, 17, 18, 19, 20, 21, 25, 27,
28, 37, 38, 40 and 41, C.I. Reactive Green 5 and 7, and C.I. Reactive
Brown 1, 7 and 16;
food dyes, for example, C.I. Food Black 1 and 2, C.I. Food Yellow 3, 4 and
5, C.I. Food Red 2, 3, 7, 9, 14, 52, 87, 92, 94, 102, 104, 105 and 106,
C.I. Food Violet 2, C.I. Food Blue 1 and 2, and C.I. Food Green 2 and 3.
Further, it is also possible to utilize Kayaset Black 009A, Direct Deep
Black XA, and Direct Special Black AXN, manufactured by Nippon Kayaku Co.,
Ltd., Bayscript Black SP Liquid, Levacell Turquoise Blue KS-6GLL and
Pyranine, manufactured by Bayer Japan Ltd., JI. BK-2 and JI. BK-3,
manufactured by Sumitomo Chemical Co., Ltd., JPK-81L, JPX127L, JPK-139 and
C.I. Fluorescent Brightening Agent 14, 22, 24, 32, 84, 85, 86, 87, 90,
134, 166, 167, 169, 175, 176 and 177, manufactured by Orient Chemical
Industries, Ltd. and other dyes.
According to a preferred embodiment of the present invention, examples of
dyes which may be added to the ink composition include water-soluble dyes
represented by the following formulae (I) and (II):
##STR1##
wherein A represents POOM or COOM, X and Y each independently represent an
alkoxy or alkyl group, M represents an alkali metal, H, or NH.sub.4 or an
organic amine; and
##STR2##
wherein M represents an alkali metal, H, or NH.sub.4 or an organic amine,
m is 1 or 2 and n is 0 or 1.
The addition of these dyes can advantageously improve the print density.
Even in the case of a pigment which provides a reddish, bluish, or
yellowish black, the use thereof in combination with the dye can create a
better black color.
The amount of the water-soluble dye represented by the formula (I) or (II)
is preferably 50 to less than 200% by weight based on the pigment.
Preferred specific examples of the water-soluble dyes represented by the
formulae (I) and (II) include the following dyes (1) to (23):
##STR3##
According to a preferred embodiment of the present invention, the ink
composition may further comprise a surfactant and/or a regulated
polymerization type water-soluble resin. In the ink composition of the
present invention, the surfactant and the regulated polymerization type
water-soluble resin function to further accelerate or stabilize the
dispersion of the pigment. Further, in the ink jet recording method, the
surfactant and the regulated polymerization type water-soluble resin can
improve the color density of the print and ejection stability at high
temperatures.
Examples of surfactants usable herein include those described above.
Regulated polymerization type water-soluble resins usable in the present
invention include alternating copolymers and block copolymers which have a
portion having at the terminal or intermediate of the molecule a
functional group bondable, by a hydrogen bond or a covalent bond, to the
functional group of a pigment and a hydrophilic group at the terminal of
the molecule and have a regularly arranged molecular structure. Specific
examples of regulated polymerization type resins usable herein include
Solsperse S3000, S5000, S9000, S12000, S13240, S13440, S20000, S22000,
S24000 GR, S26000, S27000, and S28000, manufactured by Zeneca Co., Ltd.,
Osaka-shi, Osaka.
Reaction solution and ink jet recording method using two liquids
The ink composition according to the present invention may form an image by
ink jet recording. Combination of the ink composition of the present
invention with the recording method using the so-called "two liquids" can
offer a better image. Specifically, an image having no significant
bleeding or feathering can be realized even on plain paper. Further, as
compared with the sole use of the ink composition of the present
invention, the combination of the ink composition of the present invention
with the ink jet recording method using two liquids can offer improved
print density.
The ink jet recording method according to the present invention involves
the step of depositing a reaction solution containing a reactant and the
above ink composition onto a recording medium. The term "reactant" used
herein refers to an agent which can break the state of dispersion and/or
dissolution of the pigment and can agglomerate the pigment.
In the recording method using two liquids, like the ink jet recording
method according to the present invention, a good print can be realized by
contact of the reaction solution with the ink composition. Specifically,
upon contact of the reaction solution with the ink composition, the
reactant contained in the reaction solution-breaks the state of dispersion
of the pigment and other components in the ink composition, leading to
agglomeration of the pigment and the like. The agglomerate is considered
to deposit onto the recording medium, realizing a print having high color
density and no significant bleeding or feathering and unevenness. Further,
advantageously, in the case of a color image, uneven color-to-color
intermixing in the region of boundary between different colors, that is,
color bleeding, can be effectively prevented.
Therefore, also in the present invention, the reaction solution is brought
into contact with the ink composition. In this case, the step of ejecting
droplets of the ink composition onto the recording medium to record an
image may be conducted either before or after the deposition of the
reaction solution onto the recording medium, with the practice of the step
of recording after the deposition of the reaction solution being
preferred.
The reaction solution may be selectively deposited on only the areas where
the ink composition is deposited, or alternatively may be deposited on the
whole area of the recording medium. The former method can minimize the
consumption of the reaction solution and, hence, is cost-effective. In the
former method, however, both the reaction solution and the ink composition
should be deposited onto a contemplated position with certain accuracy. On
the other hand, in the latter method, the requirement for the accuracy on
the position of the deposition of the reaction solution and the ink
composition is reduced as compared with the former method. However, the
latter method is disadvantageous in that a large amount of the reaction
solution is deposited onto the whole area of the recording medium, causing
paper, when used as the recording medium, to be likely to curl upon
drying. Therefore, which method is used may be determined by taking into
consideration a combination of the ink composition with the reaction
solution. When the former method is adopted, the reaction solution can be
deposited by the ink jet recording method.
The reaction solution used in the present invention comprises a reactant
which can break the state of dispersion of the colorant and the like in
the ink composition and can agglomerate the colorant component and the
like.
Reactants usable in the present invention include cationic compounds, for
example, primary, secondary, tertiary, and quaternary amines and compounds
having in molecule ammonium, phosphorus, and phosphonium. Further,
polyallylamine, polyethyleneimine, polyvinyl pyrrolidone, polyvinyl
imidazole, polyvinyl pyridine, ionene, and polydialkylallylammonium salt
are also usable. Further examples of cationic compounds usable herein
include those containing as a cation species a metal ion of an alkali
metal, such as lithium, sodium, or potassium, an alkaline earth metal,
such as magnesium or calcium, aluminum, zinc, chromium, copper, nickel, or
iron, for example, salts of the above cation species with carbonic acid,
bicarbonic acid, oxalic acid, succinic acid, asparagic acid, ascorbic
acid, gluconic acid, glutaric acid, glutamic acid, lactic acid, butyric
acid, isobutyric acid, benzoic acid, oleic acid, glyceric acid, molybdic
acid, palmitic acid, phosphonic acid, patetonic acid, phosphinic acid,
phthalic acid, formic acid, acetic acid, sulfurous acid, nitrous acid,
nitric acid, phosphoric acid, phosphorous acid, pyrophosphoric acid,
salicylic acid, silicic acid, borosilicic acid, capronic acid, capric
acid, caprylic acid, lauric acid, malonic acid, maleic acid,
metabisulfite, myristic acid, stearic acid, tartaric acid, bitartaric
acid, aluminic acid, boric acid, hydrochloric acid, and sulfuric acid.
Further, commercially available products may be used as the reactant, and
specific examples thereof include Sanfix (manufactured by Sanyo Chemical
Industries, Ltd.), Protex and Fix (manufactured by Kuroda-Kako Co, Ltd.),
Morin Fix Conc (manufactured by Morin Chemical Industries, Ltd., Amigen
(manufactured by Dai-Ichi Kogyo Yakuhin K.K.), Epomin (manufactured by
Nippon Shokubai Kagaku Kogyo Co., Ltd.), Fixoil (manufactured by Meisei
Chemical Works Co., Ltd.), Neofix (manufactured by Nicca Chemical Co.,
Ltd.), Polyamine Sulfone (manufactured by Nitto Boseki Co., Ltd.), Polyfix
(manufactured by Showa High Polymer Co., Ltd.), Nikafix (manufactured by
Nippon Carbide Industries Co., Ltd.), Levogen (manufactured by Bayer), and
Kaimen (manufactured by DIC-Hercules Chemicals Inc.).
In the present invention, the amount of the reactant added is preferably
about 0.5 to 40% by weight, more preferably about 1 to 10% by weight. When
the reactant contains a metal ion, the content of the metal ion is
preferably about 0.01 to 1 mol/kg, more preferably 0.03 to 0.3 mol/kg.
Preferably, the reaction solution used in the ink jet recording method
according to the present invention contains one member or a mixture of at
least two members selected from the group consisting of glycol ethers, for
example, diethylene glycol mono-n-butyl ether, triethylene glycol
mono-n-butyl ether, propylene glycol mono-n-butyl ether, and dipropylene
glycol mono-n-butyl ether. The amount of the glycol ether added is
preferably about 3 to 30% by weight, more preferably about 5 to 10% by
weight. The addition of the glycol ether can improve the penetration of
the reaction solution into paper, resulting in reduced bleeding or
feathering. Further, since the glycol ether has low vapor pressure, it is
possible to prevent the ink from drying at the front end of the nozzle of
the ink jet recording head. Furthermore, when recording using the ink
composition is conducted with the reaction solution being penetrated into
paper to some extent, an improvement in the quality of the record can be
attained by virtue of the compatibility with the glycol ether as a
component of the ink composition.
According to a preferred embodiment of the present invention, the reaction
solution used in the ink jet recording method according to the present
invention may suitably contain a component which may be added to the above
ink composition. The amount of such a component added may be the same as
that in the case of the addition to the above ink composition.
In order to avoid the influence of the reaction solution on printed letters
or figures, the reaction solution used in the present invention is
preferably colorless or light-colored so that, in general, the color of
the reaction solution cannot be perceived by the human eye. In this case,
preferably, the reaction solution is deposited onto the recording medium
before printing of a black ink and/or a color ink.
Alternatively, a colorant component may be added to the reaction solution
so that the reaction solution can serve also as a color ink composition.
When the reaction solution functions also a color ink composition, the dye
used in combination with the reaction solution should not cause
agglomeration or thickening. In general, dyes having a polar group, such
as a carboxyl group, is likely to be agglomerated by a metal ion. The
present inventors have confirmed that the agglomeration of such dyes can
be prevented by introducing a hydrophilic group such as a sulfone group.
Therefore, even dyes which as such cannot be utilized in the present
invention often become usable by the introduction of a functional group
while giving consideration to the water resistance of the dyes. Specific
examples of dyes which are usable or become usable by the introduction of
a functional group include those cited above in connection with the ink
composition.
Incorporation of a reactive component into a color ink is preferred from
the viewpoint of preventing mixing between a black ink and a color ink,
that is, bleeding.
According to a preferred embodiment of the present invention, the amount of
the ink composition is preferably 50 to 200%, more preferably 75 to 150%,
based on the amount of the reaction solution.
Further, according to a preferred embodiment of the present invention, the
time taken from the deposition of the reaction solution onto the recording
medium to the initiation of the printing of the ink composition is
preferably not more than 3 sec, more preferably not more than 1 sec, still
more preferably not more than 0.1 sec. When this time interval is short,
an agglomeration reaction of the pigment in the ink composition with the
reaction solution is facilitated. At the same time, the color density is
increased resulting in improved record quality.
Further, according to the recording method of the present invention, when
the reaction solution serves also as the color ink composition, the
deposition may be performed once or a plurality of times in a single
color, or alternatively may be performed once or a plurality of times
after mixing of a plurality of colors. This can change the color of the
undercoat, enabling the final color density after recording the ink
composition to be brought to a desired one. For example, blue created by
mixing cyan and magenta, green created by mixing cyan and yellow, red
created by mixing magenta and yellow, and a color created by mixing all of
cyan, magenta, and yellow may be used as an undercoat to improve the final
color density.
An ink jet recording apparatus for practicing the ink jet recording method
using two liquids according to the present invention will be described
with reference to the accompanying drawings.
FIG. 1 shows an embodiment of an ink jet recording apparatus, wherein an
ink composition and a reaction solution are placed in a tank and the ink
composition and the reaction solution are supplied into a recording head
through an ink tube. Specifically, a recording head 1 is communicated with
an ink tank 2 through an ink tube 3. In this case, the interior of the ink
tank 2 is partitioned into a chamber for an ink composition, optionally a
plurality of chambers for a plurality of color ink compositions, and a
chamber for a reaction solution.
The recording head 1 is moved along a carriage 4 by means of a timing belt
6 driven by a motor 5. On the other hand, paper 7 as a recording medium is
positioned by means of a platen 8 and a guide 9 so as to face the
recording head 1. In this embodiment, a cap 10 is provided. A suction pump
11 is connected to the cap 10 so that the so-called "cleaning operation"
can be performed. The sucked ink composition is collected through a tube
12 into a waste ink tank 13.
FIG. 2 is an enlarged view of a nozzle face of the recording head 1. A
nozzle face of the reaction solution is indicated by 1b, and a nozzle 21,
through which the reaction solution is ejected, is provided in
longitudinal direction. On the other hand, a nozzle face for an ink
composition is indicated by 1c, and a yellow ink composition, a magenta
ink composition, a cyan ink composition, and a black ink composition are
ejected respectively through nozzles 22, 23, 24, and 25.
An ink jet recording method using the recording head shown in FIG. 2 will
be described with reference to FIG. 3. The recording head 1 is moved in a
direction indicted by an arrow A. During the movement of the recording
head 1, the reaction solution is ejected from the nozzle face 1 to form a
reaction solution deposited area 31 in a band form on the recording medium
7. The recording medium 7 is transferred by a predetermined length in the
direction of feed of the paper indicated by an arrow B, during which time
the recording head 1 is moved in a direction opposite to that indicated by
the arrow A shown in the drawing and is returned to the left end of the
recording medium 7. Then, the recording head 1 prints the ink composition
in the reaction solution deposited area where the reaction solution has
been deposited, thereby forming a printed area 32.
Alternatively, as shown in FIG. 4, in the recording head 1, all the nozzles
may be arranged in the lateral direction. In the drawing, 41a and 41b
designate nozzles for ejecting a reaction solution, and a yellow ink
composition, a magenta ink composition, a cyan ink composition, and a
black ink composition are ejected respectively through nozzles 42, 43, 44,
and 45. In the recording head according to this embodiment, since the
recording head 1 can perform printing in both directions in the
reciprocation of the recording head on the carriage, printing at a higher
speed than that in the embodiment shown in FIG. 2 can be expected.
Further, the ink jet recording apparatus according to the present invention
may be constructed so that the replenishment of the ink composition is
conducted by replacing a cartridge as the ink tank. Alternatively, it may
be constructed so that the ink tank is integral with the recording head.
A preferred embodiment of the ink jet recording apparatus utilizing such an
ink tank is shown in FIG. 5. In the drawing, the same members as used in
the apparatus shown in FIG. 1 have the same reference numerals. In the
embodiment shown in FIG. 5, recording heads 1a and 1b are integral
respectively with ink tanks 2a and 2b. An ink composition and a reaction
solution are ejected respectively through the recording heads 1a and 1b.
Basically, printing may be conducted in the same manner as described above
in connection with the apparatus shown in FIG. 1. Further, in this
embodiment, the recording head 1a is moved together with the ink tank 2a
on a carriage 4, while the recording head 1a is moved together with the
ink tank 2b on the carriage 4.
When an ink having a relatively high content of solid matter, such as a
pigment, like the ink of the present invention, is used, the ink is likely
to be dried at the front end of a nozzle, through which the ink has not
been ejected for a long period of time. This is in turn likely to cause
thickening resulting in disturbed prints. In this case, the ink
composition is preferably moved to vibrate at the front end of the nozzle
to such an extent that it is not ejected as droplets through the nozzle.
By this vibration of the ink, the ink is agitated permitting the ink to be
stably ejected. The vibration of the ink can be achieved by applying a
pressure using pressure means for ejecting the ink in a controlled manner
so as not to cause ejection of the ink. The use of an electrostrictive
element as the pressure means is preferred from the viewpoint of easy
control. When this mechanism is used, the concentration of the pigment in
the ink can be increased, enabling a pigment ink having high color density
to be stably ejected.
Further, the vibration of the ink composition is effective for an ink
composition having a pigment content of about 5 to 15% by weight,
preferably about 7 to 10% by weight.
According to another preferred embodiment of the present invention, The ink
jet recording apparatus is characterized by having such a construction
that a polyurethane foam is packed into an ink cartridge for accommodating
black and color inks so that the ink comes into contact with the urethane
foam. In this case, a glycol ether and an acetylene glycol surfactant
which may be preferably used in the present invention may be adsorbed on
the urethane foam. Therefore, preferably, these compounds may be added in
an excessive amount in consideration of the amount of the compounds
adsorbed on the urethane foam. Further, the urethane foam can ensure a
negative pressure when the ink is one which may be preferably used in the
present invention. Furthermore, by virtue of the urethane foam,
decomposition or occurrence of an undesired material due to components of
the ink used in the present invention, which is causative of clogging, is
less likely to occur. In the urethane foam, a curing catalyst containing a
metal salt or cationic catalyst is not used, and the use of urethane foam
comprising a polyfunctional isocyanate, such as tolylene diisocyanate or
m-xylene diisocyanate, and a glycol having an average molecular weight of
about 300 to 3000 compound, such as polypropylene glycol or polyethylene
glycol, or a compound having a plurality of hydroxyl groups, such as
glycerin, pentaerythritol, dipentaerythritol, neopentyl glycol, propylene
glycol, 1,3-butanediol, 1,4-butanediol, or a 1,5-pentanediol, is preferred
from the viewpoint of ensuring the negative pressure by virtue of good
stability of the form of the foam and chemical stability.
EXAMPLES
The present invention will be described with reference to the following
examples, though it is not limited to these examples only.
In the examples, the following abbreviations were used.
PGmBE: propylene glycol mono-n-butyl ether
DEGmBE: diethylene glycol mono-n-butyl ether
DPGmBE: dipropylene glycol mono-n-butyl ether
TEGmBE: triethylene glycol mono-n-butyl ether
PGmME: propylene glycol monomethyl ether
DMI: 1,3-dimethyl-2-imidazolidinone
DPGmME: dipropylene glycol monomethyl ether
MPD:2-methyl-2,4-pentanediol
DEGmtBE: diethylene glycol-mono-t-butyl ether
TEGmME: triethylene glycol monomethyl ether
In the following examples and comparative examples, "%" is by weight.
Example A
In Example A, a carbon black having an average particle diameter of 60 to
150 .mu.m, of which the surface has been carboxylated by chemical
treatment, was used as a water-soluble pigment.
Water as the balance contained 0.1 to 1% of Proxel XL-2 as an agent for
preventing the corrosion of the ink and 0.001 to 0.05% of benzotriazole as
an agent for preventing the corrosion of an ink jet head member.
The following ink compositions were prepared.
______________________________________
Example A1
Water-soluble pigment
5.0%
(average particle diameter: 90 .mu.m)
PGmBE 5.0%
DEGmBE 7.0%
Glycerin 6.0%
1,4-Butanediol 5.0%
Surfynol 104 1.0%
Ion-exchanged water Balance
Example A2
Water-soluble pigment
4.5%
DPGmBE 5.0%
TEGmBE 10.0%
Dipropylene glycol 5.0%
Urea 5.0%
Surfynol TG 1.2%
Fluorosurfactant 0.1%
Ion-exchanged water Balance
Example A3
Water-soluble pigment
5.5%
PGmBE 5.0%
DEGmBE 10.0%
Propylene glycol 7.0%
Triethylene glycol 3.0%
1,5-Pentanediol 5.0%
Surfynol TG 1.4%
Ion-exchanged water Balance
Example A4
Water-soluble pigment
5.0%
DEGmBE 10.0%
1,6-Hexanediol 5.0%
Tripropylene glycol 2.0%
DMI 2.0%
Surfynol 104 0.8%
Surfynol 465 0.4%
Ion-exchanged water Balance
______________________________________
The following reaction solutions were prepared.
______________________________________
Reaction solution A1
Direct Blue 199 3.0%
PGmBE 5.0%
DPGmME 10.0%
MPD 3.0%
Trimethylolpropane
3.0%
Magnesium nitrate 3.0%
Surfynol TG 1.2%
Triethanolamine 0.9%
Ion-exchanged water
Balance
Reaction solution A2
Acid Red 289 3.5%
PGmBE 5.0%
DPGmBE 2.0%
DEGmBE 10.0%
Neopentyl glycol 5.0%
Calcium L-ascorbate
3.0%
Surfynol TG 0.5%
Surfynol 104 0.5%
Ion-exchanged water
Balance
Reaction solution A3
Direct Yellow 132 5.0%
TEGmBE 10.0%
Glycerin 5.0%
Trimethylolpropane
5.0%
Trimethylolethane 5.0%
Magnesium acetate 2.0%
Calcium acetate 1.0%
Surfynol 465 1.0%
Surfynol TG 0.6%
Triethanolamine 0.1%
Ion-exchanged water
Balance
Reaction solution A4
Bonjet Black 817 5.5%
DPGmBE 5.0%
DEGmtBE 5.0%
DEGmBE 5.0%
Diethylene glycol 5.0%
Tetrapropylene glycol
5.0%
Magnesium benzoate
2.5%
Surfynol 104 1.0%
Ion-exchanged water
Balance
Reaction solution A5
TEGmBE 10.0%
Glycerin 5.0%
Trimethylolpropane
5.0%
Trimethylolethane 5.0%
Magnesium acetate 2.0%
Calcium acetate 1.0%
Surfynol 465 1.0%
Surfynol TG 0.6%
Triethanolamine 0.1%
Ion-exchanged water
Balance
______________________________________
Then, the following comparative ink compositions were prepared.
In the comparative ink compositions, a pigment dispersion prepared by
dispersing a carbon black having an average particle diameter of 60 to 150
.mu.m with the aid of a styrene-acrylic dispersant was used.
______________________________________
Comparative Example A1
Pigment dispersion 5.0%
TEGmME 10.0%
Ethylene glycol 8.0%
Dispersant 3.0%
DEGmME 7.0%
Ion-exchanged water
Balance
Comparative Example A2
Pigment dispersion 5.5%
Glycerin 10.0%
Diethylene glycol 10.0%
Dispersant 5.0%
Ion-exchanged water
Balance
Comparative Example A3
Pigment dispersion 5.5%
Diethylene glycol 10.0%
Surfynol 465 1.0%
Ion-exchanged water
Balance
______________________________________
Printing Test
Printing was performed, on various recording papers listed in the following
Table 1, using the ink compostions prepared in Examples A1 to A4 and
Comparative Examples A1 to A3 by means of an ink jet printer MJ-7000V2C by
Seiko Espon Corporation.
Further, prior to printing using the ink compositions, solid printing (100%
duty) of the reaction solution A5 was performed by means of the same head
as the ink jet printer MJ-700V2C onto the recording medium, and printing
using the ink compositions was performed in the same manner as described
above.
These records were evaluated for "bleeding" and "feathering." In this case,
the term "bleeding" used herein refers to fine uneven penetration of ink,
which lowers the circularity of the dot, and the term "feathering" used
herein refers to linear uneven penetration of ink extending in a streak
form along the fibers of the paper. These phenomena were visually
inspected to evaluate the influence thereof on the image. The results were
evaluated according to the following criteria:
.circleincircle.(excellent): Not influenced the image.
.largecircle.(good): Influenced the image but pose no problem in practical
use of the ink composition.
.DELTA.: Influenced the image and pose problem in practical use of the ink
composition.
X: Influenced the image, rendering the ink composition unsuitable for
practical use.
The results were as tabulated in Table 1.
TABLE 1
__________________________________________________________________________
Ex. A Comp. Ex. A
Undercoat not
Undercoat
Undercoat not
Undercoat
Test provided
provided
provided
provided
item
Type of paper
1 2 3 4 1 2 3 4 1 2 3 1 2 3
__________________________________________________________________________
Bleed-
Conqueror Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.smallcircle.
.circleincircle.
.smallcircle.
.circleincircle.
.circleincircle.
.smallcircle.
ing Favorit Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.smallcircle.
.smallcircle.
.smallcircle.
.circleincircle.
.circleincircle.
Modo Copy Paper
.smallcircle.
.smallcircle.
.smallcircle.
.smallcircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x .DELTA.
x .DELTA.
.circleincircle.
.DELTA.
Rapid Copy Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.smallcircle.
.smallcircle.
.smallcircle.
.circleincircle.
.circleincircle.
EPSON EPP Paper
.smallcircle.
.smallcircle.
.smallcircle.
.smallcircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x .DELTA.
x .DELTA.
.circleincircle.
.DELTA.
Xerox P Paper
.smallcircle.
.smallcircle.
.smallcircle.
.smallcircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x .DELTA.
x .DELTA.
.circleincircle.
.DELTA.
Xerox 4024 Paper
.smallcircle.
.circleincircle.
.smallcircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.smallcircle.
.DELTA.
.smallcircle.
.circleincircle.
.smallcircle.
Xerox 10 Paper
.circleincircle.
.circleincircle.
.smallcircle.
.smallcircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
.DELTA.
.smallcircle.
.smallcircle.
.smallcircle.
Neenha Bond
.smallcircle.
.smallcircle.
.smallcircle.
.smallcircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x .DELTA.
.DELTA.
.DELTA.
.smallcircle.
.smallcircle.
Paper
Ricopy 6200
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
.DELTA.
.smallcircle.
.smallcircle.
.smallcircle.
Paper
Yamayuri Paper
.smallcircle.
.smallcircle.
.smallcircle.
.smallcircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x .DELTA.
x .DELTA.
Xerox R Paper
.smallcircle.
.smallcircle.
.smallcircle.
.smallcircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x .DELTA.
x .DELTA.
Feath-
Conqueror Paper
.circleincircle.
.circleincircle.
.circleincircle.
.smallcircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x .DELTA.
x .DELTA.
.smallcircle.
.DELTA.
ering
Favorit Paper
.circleincircle.
.circleincircle.
.smallcircle.
.smallcircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
.DELTA.
.smallcircle.
.smallcircle.
.smallcircle.
Modo Copy Paper
.smallcircle.
.smallcircle.
.smallcircle.
.smallcircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
x .DELTA.
.smallcircle.
.DELTA.
.smallcircle.
Rapid Copy Paper
.smallcircle.
.smallcircle.
.smallcircle.
.smallcircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x .DELTA.
.DELTA.
.DELTA.
.smallcircle.
Xerox P Paper
.smallcircle.
.smallcircle.
.smallcircle.
.smallcircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x .DELTA.
x .DELTA.
.smallcircle.
.DELTA.
Xerox 4024 Paper
.smallcircle.
.smallcircle.
.smallcircle.
.smallcircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x .DELTA.
x .DELTA.
Yamayuri Paper
.smallcircle.
.smallcircle.
.smallcircle.
.smallcircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x .DELTA.
x .DELTA.
Xerox R Paper
.smallcircle.
.smallcircle.
.smallcircle.
.smallcircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x .DELTA.
.DELTA.
.DELTA.
__________________________________________________________________________
In Table 1, Ricopy 6200 Paper, Yamayuri Paper, and Xerox R Paper are
recycled papers.
Thereafter, the reaction solutions A1 to A4 were printed on the recording
media, and printing was performed using the ink composition of Example A1.
Printing was performed by means of the same printer as used above.
The OD values of the prints thus obtained were measured. The results were
as shown in Table 2.
TABLE 2
______________________________________
Reaction solution
Type of paper
A1 A2 A3 A4 None
______________________________________
Conqueror Paper
1.40 1.39 1.35 1.44 1.17
Favorit Paper
1.43 1.42 1.37 1.47 1.20
Modo Copy Paper
1.43 1.43 1.37 1.48 1.21
Rapid Copy Paper
1.45 1.44 1.39 1.49 1.21
EPSON EPP Paper
1.40 1.38 1.32 1.42 1.14
Xerox P Paper
1.43 1.42 1.35 1.44 1.17
Xerox 4024 Paper
1.38 1.36 1.32 1.40 1.08
Xerox 10 Paper
1.34 1.31 1.30 1.34 1.05
Neenha Bond Paper
1.36 1.35 1.33 1.39 1.08
Ricopy 6200 Paper
1.41 1.40 1.42 1.49 1.23
Yamayuri Paper
1.50 1.48 1.46 1.53 1.34
Xerox R Paper
1.40 1.40 1.34 1.45 1.17
______________________________________
Example B
In the following examples, carbon blacks having an average particle
diameter of 80 to 130 .mu.m, of which the surface has been chemically
treated to graft thereon functional groups, such as a carbonyl group, a
carboxyl group, and a hydroxyl group, were used as a water-soluble
pigment. Numerical values within the parentheses in water-soluble pigments
1 to 8 are the average particle diameters (.mu.m) of the carbon blacks
Water as the balance contained 0.1 to 1% of Proxel XL-2 as an agent for
preventing the corrosion of the ink and 0.001 to 0.05% of benzotriazole as
an agent for preventing the corrosion of an ink jet head member.
The following ink compositions were prepared.
______________________________________
Example B1
Water-soluble pigment 1 (105)
5.0%
Food Black 2 1.0%
PGmBE 5.0%
DEGmBE 7.0%
Glycerin 6.0%
1,4-Butanediol 5.0%
Surfynol 104 1.0%
Triethanolamine 0.8%
Ion-exchanged water Balance
Example B2
Water-soluble pigment 2 (85)
4.5%
Direct Black 154 1.0%
DPGmBE 5.0%
TEGmBE 10.0%
Dipropylene glycol 5.0%
Urea 5.0%
Surfynol TG 1.2%
Fluorosurfactant 0.1%
Ion-exchanged water Balance
Example B3
Water-soluble pigment 3 (120)
5.5%
Acid Black 63 0.5%
PGmBE 5.0%
DEGmBE 10.0%
Propylene glycol 7.0%
Triethylene glycol 3.0%
1,5-Pentanediol 5.0%
Surfynol TG 1.4%
Potassium hydroxide 0.1%
Ion-exchanged water Balance
Example B4
Water-soluble pigment 4 (80)
5.0%
Bayscript Black SPL 1.0%
DEGmBE 10.0%
1,6-Hexanediol 5.0%
Tripropylene glycol 2.0%
DMI 2.0%
Surfynol 104 0.8%
Surfynol 465 0.4%
Sodium benzoate 0.1%
Ion-exchanged water Balance
Example B5
Water-soluble pigment 5 (95)
5.0%
Direct Black 11 1.0%
PGmBE 5.0%
DPGmME 10.0%
MPD 3.0%
Trimethylolpropane 3.0%
Surfynol TG 1.2%
Triethanolamine 0.9%
Ion-exchanged water Balance
Example B6
Water-soluble pigment 6 (100)
5.0%
Direct Black 171 1.0%
PGmBE 5.0%
DPGmBE 2.0%
DEGmBE 10.0%
Neopentyl glycol 5.0%
Surfynol TG 0.5%
Surfynol 104 0.5%
Ion-exchanged water Balance
Example B7
Water-soluble pigment 7 (110)
5.0%
Acid Black 24 1.0%
TEGmBE 10.0%
Glycerin 5.0%
Trimethylolpropane 5.0%
Trimethylolethane 5.0%
Surfynol 465 1.0%
Surfynol TG 0.6%
Triethanolamine 0.1%
Ion-exchanged water Balance
Example B8
Water-soluble pigment 8 (90)
5.5%
Acid Black 156 1.0%
DPGmBE 5.0%
DEGmtBE 5.0%
DEGmBE 5.0%
Diethylene glycol 5.0%
Tetrapropylene glycol
5.0%
Surfynol 104 1.0%
Ion-exchanged water Balance
______________________________________
Thereafter, the following comparative ink compositions were prepared.
In the comparative ink compositions, a dispersion prepared by dispersing a
carbon black having an average particle diameter of 90 to 110 .mu.m with
the aid of a styrene-acrylic dispersant was used as a pigment dispersion.
Numerical values within the parentheses in the pigment dispersions are
average particle diameters of the carbon blacks.
______________________________________
Comparative Example B1
Pigment dispersion (90)
5.0%
TEGmME 10.0%
Ethylene glycol 8.0%
Dispersant 3.0%
DEGmME 7.0%
Ion-exchanged water
Balance
Comparative Example B2
Pigment dispersion (100)
5.5%
Glycerin 10.0%
Diethylene glycol 10.0%
Dispersant 5.0%
Ion-exchanged water
Balance
Comparative Example B3
Pigment dispersion (110)
5.5%
Diethylene glycol 10.0%
Surfynol 465 1.0%
Ion-exchanged water
Balance
______________________________________
Printing test
Prints obtained using the above ink compositions were evaluated in the same
manner as in Example A. In this case, no reaction solution was used, and
prints obtained using the ink compositions alone were evaluated.
The results were as shown in the following Table 3.
TABLE 3
__________________________________________________________________________
Test Ex. B Comp. Ex. B
item
Type of paper
1 2 3 4 5 6 7 8 1 2 3
__________________________________________________________________________
Bleed-
Conqueror Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.smallcircle.
.smallcircle.
.circleincircle.
ing Favorit Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
.smallcircle.
Modo Copy Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x .DELTA.
Rapid Copy Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
.smallcircle.
EPSON EPP Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x .DELTA.
Xerox P Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x .DELTA.
Xerox 4024 Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
.smallcircle.
Xerox 10 Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
.DELTA.
Neenha Bond
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x .DELTA.
Paper
Ricopy 6200
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
.DELTA.
Paper
Yamayuri Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Xerox R Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Feath-
Conqueror Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x .DELTA.
ering
Favorit Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
.DELTA.
Modo Copy Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
x
Rapid Copy Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Xerox P Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x .DELTA.
Xerox 4024 Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Yamayuri Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Xerox R Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
__________________________________________________________________________
The OD values of the prints using the above ink compositions were evaluated
in the same manner as in Example A. In this case, no reaction solution was
used, and prints obtained using the ink compositions alone were evaluated.
The results were as shown in the following Table 4.
TABLE 4
__________________________________________________________________________
Ex. Comp. Ex.
B1 B2 B3 B4 B5 B6 B7 B8 B1 B2 B3
__________________________________________________________________________
Conqueror
1.35
1.34
1.36
1.38
1.35
1.36
1.37
1.39
1.15
1.12
1.14
Paper
Favorit
1.37
1.36
1.39
1.41
1.36
1.37
1.38
1.40
1.16
1.13
1.15
Paper
Modo Copy
1.34
1.34
1.36
1.36
1.34
1.33
1.34
1.38
1.13
1.11
1.12
Paper
Rapid Copy
1.33
1.33
1.32
1.34
1.33
1.33
1.35
1.36
1.14
1.12
1.13
Paper
Xerox P
1.32
1.31
1.32
1.33
1.32
1.33
1.34
1.34
1.10
1.09
1.10
Paper
Xerox 4024
1.30
1.30
1.31
1.32
1.31
1.30
1.32
1.32
1.08
1.07
1.10
Paper
Yamayuri
1.40
1.39
1.40
1.41
1.37
1.35
1.39
1.42
1.17
1.17
1.14
Paper
Xerox R
1.38
1.36
1.39
1.38
1.35
1.38
1.38
1.40
1.16
1.15
1.12
Paper
__________________________________________________________________________
In Examples B1 to B8, the addition of saccharides to the ink compositions
resulted in an about 10 to 30% improvement in resumption of successful
printing from clogging of the nozzle
Example C
In the following examples, a pigment dispersion was prepared by dispersing
a carbon black having an average particle diameter of 10 to 300 nm and a
degree of dispersion of not more than 10 with a surfactant and/or a
water-soluble resin prepared by regulated polymerization. The carbon black
had been subjected to surface treatment to bond carbonyl, carboxyl,
hydroxyl and the like onto the surface thereof, permitting the pigment to
be dispersed and/or dissolved in water without the aid of any dispersant.
Numerical values within the parentheses in pigment dispersions 1 to 8 are
the average particle diameters (nm) of the carbon blacks
Water as the balance contained 0.1 to 1% of Proxel XL-2 as an agent for
preventing the corrosion of the ink and 0.001 to 0.05% of benzotriazole as
an agent for preventing the corrosion of an ink jet head member.
______________________________________
Example C1
Pigment dispersion 1 (105)
5.0%
Solsperse 20000 1.0%
PGmBE 5.0%
DEGmBE 7.0%
Glycerin 6.0%
1,4-Butanediol 5.0%
Surfynol 104 1.0%
Triethanolamine 0.8%
Ion-exchanged water Balance
Example C2
Pigment dispersion 2 (85)
4.5%
Solsperse 27000 1.0%
DPGmBE 5.0%
TEGmBE 10.0%
Dipropylene glycol 5.0%
Urea 5.0%
Surfynol TG 1.2%
Fluorine surfactant 0.1%
Ion-exchanged water Balance
Example C3
Pigment dispersion 3 (20)
5.5%
Solsperse 20000 0.5%
Solsperse 27000 0.5%
PGmBE 5.0%
DEGmBE 10.0%
Propylene glycol 7.0%
Triethylene glycol 3.0%
1,5-Pentanediol 5.0%
Surfynol TG 1.4%
Potassium hydroxide 0.1%
Ion-exchanged water Balance
Example C4
Pigment dispersion 4 (80)
5.0%
Regulated polymerization type
1.0%
acrylic resin
DEGmBE 10.0%
1,6-Hexanediol 5.0%
Tripropylene glycol 2.0%
DMI 2.0%
Surfynol 104 0.8%
Surfynol 465 0.4%
Sodium benzoate 0.1%
Ion-exchanged water Balance
Example C5
Pigment dispersion 5 (95)
5.0%
Regulated polymerization type
1.0%
styrene/acrylic resin
PGmBE 5.0%
DPGmME 10.0%
MPD 3.0%
Trimethylolpropane 3.0%
Surfynol TG 1.2%
Triethanolamine 0.9%
Ion-exchanged water Balance
Example C6
Pigment dispersion 6 (100)
5.0%
Solsperse 20000 1.0%
Regulated polymerization type
1.0%
styrene/acrylic resin
PGmBE 5.0%
DPGmBE 2.0%
DEGmBE 10.0%
Neopentyl glycol 5.0%
Surfynol TG 0.5%
Surfynol 104 0.5%
Ion-exchanged water Balance
Example C7
Pigment dispersion 7 (150)
5.0%
Regulated polymerization type
1.0%
acrylic resin
Regulated polymerization type
1.0%
styrene/acrylic resin
TEGmBE 10.0%
Glycerin 5.0%
Trimethylolpropane 5.0%
Trimethylolethane 5.0%
Surfynol 465 1.0%
Surfynol TG 0.6%
Triethanolamine 0.1%
Ion-exchanged water Balance
Example C8
Pigment dispersion 8 (200)
5.5%
Solsperse 27000 0.5%
Regulated polymerization type
1.0%
acrylic resin
DPGmBE 5.0%
DEGmtBE 5.0%
DEGmBE 5.0%
Diethylene glycol 5.0%
Tetrapropylene glycol
5.0%
Surfynol 104 1.0%
Ion-exchanged water Balance
______________________________________
The following comparative ink compositions were prepared.
In the comparative ink compositions, a dispersion prepared by dispersing a
carbon black having an average particle diameter of 90 to 110 .mu.m with
the aid of a styrene-acrylic dispersant was used as a pigment dispersion.
Numerical values within the parentheses in the pigment dispersions are
average particle diameters of the carbon blacks.
______________________________________
Comparative Example C1
Pigment dispersion 9 (90)
5.0%
TEGmME 10.0%
Ethylene glycol 8.0%
Dispersant 3.0%
DEGmME 7.0%
Ion-exchanged water Balance
Comparative Example C2
Pigment dispersion 10 (100)
5.5%
Glycerin 10.0%
Diethylene glycol 10.0%
Dispersant 5.0%
Ion-exchanged water Balance
Comparative Example C3
Pigment dispersion 11 (110)
5.5%
Diethylene glycol 10.0%
Surfynol 465 1.0%
Ion-exchanged water Balance
______________________________________
Printing test
Prints obtained using the above ink compositions were evaluated in the same
manner as in Example A. In this case, no reaction solution was used, and
prints obtained using the ink compositions alone were evaluated.
The results were as shown in the following Table 5.
TABLE 5
__________________________________________________________________________
Ex. C Comp. Ex. C
Test
Type of paper
1 2 3 4 5 6 7 8 1 2 3
__________________________________________________________________________
Bleed-
Conqueror Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.smallcircle.
.smallcircle.
.circleincircle.
ing Favorit Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
.smallcircle.
Modo Copy Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x .DELTA.
Rapid Copy Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
.smallcircle.
EPSON EPP Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x .DELTA.
Xerox P Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x .DELTA.
Xerox 4024 Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
.smallcircle.
Xerox 10 Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
.DELTA.
Neenha Bond
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x .DELTA.
Paper
Ricopy 6200
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
.DELTA.
Paper
Yamayuri Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Xerox R Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Feath-
Conqueror Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x .DELTA.
ering
Favorit Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
.DELTA.
Modo Copy Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
x
Rapid Copy Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Xerox P Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x .DELTA.
Xerox 4024 Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Yamayuri Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Xerox R Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
__________________________________________________________________________
Example D
In the following examples, a pigment dispersion was prepared by dispersing
a carbon black having an average particle diameter of 10 to 300 nm and a
degree of dispersion of not more than 10 in a surfactant and/or a
water-soluble resin prepared by regulated polymerization. The carbon black
had been subjected to surface treatment to bond carbonyl, carboxyl,
hydroxyl and the like onto the surface thereof, permitting the pigment to
be dispersed and/or dissolved in water without the aid of any dispersant.
Numerical values within the parentheses in pigment dispersions 1 to 8 are
the average particle diameters (nm) of the carbon blacks.
Water as the balance contained 0.1 to 1% of Proxel XL-2 as an agent for
preventing the corrosion of the ink and 0.001 to 0.05% of benzotriazole as
an agent for preventing the corrosion of an ink jet head member.
In the following examples, Dyes (1) to (23) correspond to dye numbers
described above.
______________________________________
Example D1
Pigment dispersion 1 (105)
5.0%
Mixture of Dye (1) to (23)
3.0%
Solsperse 20000 1.0%
PGmBE 5.0%
DEGmBE 7.0%
Glycerin 6.0%
1,4-Butanediol 5.0%
Surfynol 104 1.0%
Triethanolamine 0.8%
Ion-exchanged water Balance
Example D2
Pigment dispersion 2 (85)
4.5%
Dye (2) 2.5%
Solsperse 27000 1.0%
DPGmBE 5.0%
TEGmBE 10.0%
Dipropylene glycol 5.0%
Urea 5.0%
Surfynol TG 1.2%
Fluorosurfactant 0.1%
Ion-exchanged water Balance
Example D3
Pigment dispersion 3 (20)
5.5%
Mixture of Dye (1) to (5)
3.0%
Solsperse 20000 0.5%
Solsperse 27000 0.5%
PGmBE 5.0%
DEGmBE 10.0%
Propylene glycol 7.0%
Triethylene glycol 3.0%
1,5-Pentanediol 5.0%
Surfynol TG 1.4%
Potassium hydroxide 0.1%
Ion-exchanged water Balance
Example D4
Pigment dispersion 4 (80)
5.0%
Dye (6) 2.0%
Dye (7) 2.0%
Regulated polymerization type
1.0%
acrylic resin
DEGmBE 10.0%
1,6-Hexanediol 5.0%
Tripropylene glycol 2.0%
DMI 2.0%
Surfynol 104 0.8%
Surfynol 465 0.4%
Sodium benzoate 0.1%
Ion-exchanged water Balance
Example D5
Pigment dispersion 5 (95)
3.0%
Dye (1) 6.0%
Regulated polymerization type
1.0%
styrene/acrylic resin
PGmBE 5.0%
DPGmME 10.0%
MPD 3.0%
Trimethylolpropane 3.0%
Surfynol TG 1.2%
Triethanolamine 0.9%
Ion-exchanged water Balance
Example D6
Pigment dispersion 6 (100)
5.0%
Dye (3) 3.5%
Solsperse 20000 1.0%
Regulated polymerization type
1.0%
styrene/acrylic resin
PGmBE 5.0%
DPGmBE 2.0%
DEGmBE 10.0%
Neopentyl glycol 5.0%
Surfynol TG 0.5%
Surfynol 104 0.5%
Ion-exchanged water Balance
Example D7
Pigment dispersion 7 (150)
5.0%
Mixture of Dye (4) to (8)
4.0%
Regulated polymerization type
1.0%
acrylic resin
Regulated polymerization type
1.0%
styrene/acrylic resin
TEGmBE 10.0%
Glycerin 5.0%
Trimethylolpropane 5.0%
Trimethylolethane 5.0%
Surfynol 465 1.0%
Surfynol TG 0.6%
Triethanolamine 0.1%
Ion-exchanged water Balance
Example D8
Pigment dispersion 8 (200)
5.5%
Dye (3) 1.0%
Dye (5) 2.5%
Solsperse 27000 0.5%
Regulated polymerization type
1.0%
acrylic resin
DPGmBE 5.0%
DEGmtBE 5.0%
DEGmBE 5.0%
Diethylene glycol 5.0%
Tetrapropylene glycol
5.0%
Surfynol 104 1.0%
Ion-exchanged water Balance
______________________________________
The following comparative ink compositions were prepared.
In the comparative ink compositions, a dispersion prepared by dispersing a
carbon black having an average particle diameter of 90 to 110 .mu.m with
the aid of a styrene-acrylic dispersant was used as a pigment dispersion.
Numerical values within the parentheses in the pigment dispersions are
average particle diameters of the carbon blacks.
______________________________________
Comparative Example D1
Pigment dispersion (90)
5.0%
TEGmME 10.0%
Ethylene glycol 8.0%
Dispersant 3.0%
DEGmME 7.0%
Ion-exchanged water
Balance
Comparative Example D2
Water-soluble dye 5.5%
(Food Black 2)
Glycerin 10.0%
Diethylene glycol 10.0%
2-Pyrrolidone 5.0%
Ion-exchanged water
Balance
Comparative Example D3
Pigment dispersion (110)
5.5%
Water-soluble dye 2.5%
(Food Black 2)
Diethylene glycol 10.0%
Surfynol 465 1.0%
Ion-exchanged water
Balance
______________________________________
Printing test
Prints obtained using the above ink compositions were evaluated in the same
manner as in Example A. In this case, no reaction solution was used, and
prints obtained using the ink compositions alone were evaluated.
The results were as shown in the following Table 6.
TABLE 6
__________________________________________________________________________
Test Ex. D Comp. Ex. D
item
Type of paper
1 2 3 4 5 6 7 8 1 2 3
__________________________________________________________________________
Bleed-
Conqueror Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.smallcircle.
.smallcircle.
.circleincircle.
ing Favorit Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
.smallcircle.
Modo Copy Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x .DELTA.
Rapid Copy Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
.smallcircle.
EPSON EPP Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x .DELTA.
Xerox P Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x .DELTA.
Xerox 4024 Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
.smallcircle.
Xerox 10 Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
.DELTA.
Neenha Bond
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x .DELTA.
Paper
Ricopy 6200
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
.DELTA.
Paper
Yamayuri Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Xerox R Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Feath-
Conqueror Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x .DELTA.
ering
Favorit Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
.DELTA.
Modo Copy Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.DELTA.
.DELTA.
x
Rapid Copy Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Xerox P Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x .DELTA.
Xerox 4024 Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Yamayuri Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Xerox R Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
__________________________________________________________________________
In Example D1, the pigment and dye contents were varied as follows.
Printing was performed using the ink compositions in the same manner as
described above, and the OD value of the prints was measured. The results
were as summarized in the following Table 7.
TABLE 7
______________________________________
Amount (wt %)
Pigment Dye OD
______________________________________
8.0 0.0 1.27
7.0 1.0 1.30
6.0 2.0 1.36
5.0 3.0 1.40
4.0 4.0 1.42
3.0 5.0 1.34
2.0 6.0 1.29
1.0 7.0 1.26
0.0 8.0 1.24
______________________________________
Example E
In the following examples, water-soluble pigments are carbon blacks
dispersed by surface treatment. Water-soluble pigments 1 to 4 are Microjet
CW2 manufactured by Orient Chemical Industries, Ltd., and water-soluble
pigments 5 to 8 are CW1 manufactured by Orient Chemical Industries, Ltd.
These pigments are those prepared by oxidizing the surface of a carbon
black having a particle diameter of 10 to 300 nm and a degree of
dispersion of not more than 10 to form a carbonyl group, a carboxyl group,
a hydroxyl group, a sulfonyl group or the like on the surface thereof.
Numerical values within the parentheses in pigment dispersions 1 to 8 are
the average particle diameters (nm) of the carbon blacks
Water as the balance contained 0.1 to 1% of Proxel XL-2 as an agent for
preventing the corrosion of the ink and 0.001 to 0.05% of benzotriazole as
an agent for preventing an ink jet head member.
The following black ink compositions were prepared.
______________________________________
Example E11
Water-soluble pigment 1 (105)
5.0%
PGmBE 5.0%
DEGmBE 7.0%
Glycerin 6.0%
1,5-pentanediol 5.0%
Surfynol 104 1.0%
Triethanolamine 0.8%
Ion-exchanged water Balance
Example E12
Water-soluble pigment 2 (85)
4.5%
DPGmBE 5.0%
TEGmBE 10.0%
Dipropylene glycol 5.0%
Urea 5.0%
Surfynol TG 1.2%
Fluorine surfactant 0.1%
Ion-exchanged water Balance
Example E13
Water-soluble pigment 3 (90)
5.5%
PGmBE 5.0%
DEGmBE 10.0%
Propylene glycol 7.0%
Triethylene glycol 3.0%
1,6-Hexanediol 5.0%
Surfynol TG 1.4%
Potassium hydroxide 0.1%
Ion-exchanged water Balance
Example E14
Water-soluble pigment 4 (80)
5.0%
DEGmBE 10.0%
1,6-Hexanediol 5.0%
Tripropylene glycol 2.0%
DMI 2.0%
Surfynol 104 0.8%
Surfynol 465 0.4%
Sodium benzoate 0.1%
Ion-exchanged water Balance
Example E15
Water-soluble pigment 5 (95)
3.0%
PGmBE 5.0%
DPGmME 10.0%
MPD 3.0%
Trimethylolpropane 3.0%
Surfynol TG 1.2%
Triethanolamine 0.9%
Ion-exchanged water Balance
Example E16
Water-soluble pigment 6 (100)
5.0%
PGmBE 5.0%
DPGmBE 2.0%
DEGmBE 10.0%
Neopentyl glycol 5.0%
Surfynol TG 0.5%
Surfynol 104 0.5%
Ion-exchanged water Balance
Example E17
Water-soluble pigment 7 (150)
5.0%
TEGmBE 10.0%
Glycerin 5.0%
Trimethylolpropane 5.0%
Trimethylolethane 5.0%
Surfynol 465 1.0%
Surfynol TG 0.6%
Triethanolamine 0.1%
Ion-exchanged water Balance
Example E18
Water-soluble pigment 8 (200)
5.5%
DPGmBE 5.0%
DEGmtBE 5.0%
DEGmBE 5.0%
Diethylene glycol 5.0%
Tetrapropylene glycol
5.0%
Surfynol 104 1.0%
Ion-exchanged water Balance
______________________________________
The following color ink compositions were prepared.
______________________________________
Example E21
Direct Blue 23 5.0%
Magnesium nitrate
1.0%
PGmBE 5.0%
DEGmBE 7.0%
Glycerin 6.0%
1,5-pentanediol 5.0%
Surfynol 104 1.0%
Triethanolamine 0.8%
Ion-exchanged water
Balance
Example E22
Direct Red 283 4.5%
Calcium oxalate 1.5%
DPGmBE 5.0%
TEGmBE 10.0%
Dipropylene glycol
5.0%
Urea 5.0%
Surfynol TG 1.2%
Fluorine surfactant
0.1%
Ion-exchanged water
Balance
Example E23
Direct Yellow 86 5.5%
Calcium carbonate
1.0%
PGmBE 5.0%
DEGmBE 10.0%
Propylene glycol 7.0%
Triethylene glycol
3.0%
1,6-Hexanediol 5.0%
Surfynol TG 1.4%
Potassium hydroxide
0.1%
Ion-exchanged water
Balance
Example E24
Acid Blue 9 5.0%
Magnesium succinate
1.0%
DEGmBE 10.0%
1,6-Hexanediol 5.0%
Tripropylene glycol
2.0%
DMI 2.0%
Surfynol 104 0.8%
Surfynol 465 0.4%
Sodium benzoate 0.1%
Ion-exchanged water
Balance
Example E25
Acid Red 283 3.0%
Magnesium ascorbate
1.5%
PGmBE 5.0%
DPGmME 10.0%
MPD 3.0%
Trimethylolpropane
3.0%
Surfynol TG 1.2%
Triethanolamine 0.9%
Ion-exchanged water
Balance
Example E26
Acid Yellow 23 5.0%
Calcium glutarate
1.0%
PGmBE 5.0%
DPGmBE 2.0%
DEGmBE 10.0%
Neopentyl glycol 5.0%
Surfynol TG 0.5%
Surfynol 104 0.5%
Ion-exchanged water
Balance
Example E27
Direct Blue 86 5.0%
Calcium glutamate
1.0%
TEGmBE 10.0%
Glycerin 5.0%
Trimethylolpropane
5.0%
Trimethylolethane
5.0%
Surfynol 465 1.0%
Surfynol TG 0.6%
Triethanolamine 0.1%
Ion-exchanged water
Balance
Example E28
Acid Red 35 5.5%
Magnesium lactate
1.0%
DPGmBE 5.0%
DEGmtBE 5.0%
DEGmBE 5.0%
Diethylene glycol
5.0%
Tetrapropylene glycol
5.0%
Surfynol 104 1.0%
Ion exchanged water
Balance
______________________________________
In the comparative ink compositions, a dispersion prepared by dispersing a
carbon black having an average particle diameter of 90 to 110 .mu.m with
the aid of a styrene-acrylic acid dispersant was used as a pigment
dispersion. Numerical values within the parentheses in the pigment
dispersions are average particle diameters of the carbon blacks.
______________________________________
Comparative Example E31
Pigment dispersion (90)
5.0%
TEGmME 10.0%
Ethylene glycol 8.0%
Dispersant 3.0%
DEGmME 7.0%
Ion-exchanged water
Balance
Comparative Example E32
Pigment dispersion (110)
5.5%
Water-soluble dye 2.2%
(Food Black 2)
Dispersant 1.0%
Diethylene glycol 10.0%
Surfynol 465 1.0%
Ion-exchanged water
Balance
Comparative Example E33
Water-soluble dye 5.5%
(Food Black 2)
Glycerin 10.0%
Diethylene glycol 10.0%
2-Pyrrolidone 5.0%
Ion-exchanged water
Balance
______________________________________
Printing test
The above black inks and color inks were used to form a black ink dot and a
color ink dot adjacent to each other, and the print was inspected for the
presence of color-to-color intermixing, that is, bleeding. A printer with
a modified material used in the head section of an ink jet printer MJ-900C
manufactured by Seiko Epson Corporation was used for the printing.
Recording papers listed in Table 8 were used as the recording medium.
The bleeding was visually inspected to evaluate the influence thereof on
the formed image. Evaluation criteria are as follows.
.circleincircle.(excellent): Not influenced the image.
.largecircle.(good): Influenced the image but poses no problem in practical
use of the ink composition.
.DELTA.: Influenced the image and pose problem in practical use of the ink
composition.
X: Influenced the image, rendering the ink composition unsuitable for
practical use.
The results were as tabulated in Table 8.
TABLE 8
__________________________________________________________________________
Black ink
E11
E12
E13
E14
E15
E16
E17
E18
E33
E32
E33
Color ink
E21
E22
E23
E24
E25
E26
E27
E28
E21
E22
E23
__________________________________________________________________________
Conqueror Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Favorit Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Modo Copy Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Rapid Copy Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
EPSON EPP Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Xerox P Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Xerox 4024 Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Xerox 10 Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Neenha Bond Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Ricopy 6200 Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Yamayuri Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
Xerox R Paper
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
x x x
__________________________________________________________________________
Then, color ink compositions of Examples E41 to E48 were prepared in the
same manner as in Examples E21 to E28, except that magnesium sulfate,
calcium oxalate, calcium carbonate, magnesium succinate, magnesium
ascorbate, calcium glutarate, calcium glutamate, and calcium lactate used
in respectively in Examples E21 to E28 were not added.
A reaction solution was prepared in the same manner as in Example E11,
except that polyallylamine was added instead of the water-soluble pigment.
Printing was performed using the above ink compositions and the reaction
solution. Prior to printing using the ink compositions, the reaction
solution was coated by means of MJ-900C manufactured by Seiko Epson
Corporation. Thereafter, a black dot and a color dot were formed in the
same manner as described above, and the print was inspected for the
presence of color-to-color intermixing, that is, bleeding. The results
were evaluated in the same manner as described above. Xerox 4024 paper was
used as the recording paper.
The results were as summarized in Table 9.
TABLE 9
______________________________________
Black ink
E11 E12 E13 E14 E15 E16 E17 E18
Color ink
E41 E42 E43 E44 E45 E46 E47 E48
______________________________________
Xerox 4024
.circleincircle.
.circleincircle.
.smallcircle.
.circleincircle.
.circleincircle.
.smallcircle.
.circleincircle.
.smallcircle.
______________________________________
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